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Indexed by:期刊论文

Date of Publication:2021-03-26

Journal:ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE

Volume:646

Issue:17

Page Number:1437-1443

ISSN No.:0044-2313

Key Words:Metal-organic framework; Metal-organic framework; Structural transformation; Metal-organic framework; Structural transformation; Transmetalation; Metal-organic framework; Structural transformation; Transmetalation; HKUST-1; Metal-organic framework; Structural transformation; Transmetalation; HKUST-1; Desulfurization

Abstract:[Co-2(BTC)(Cl)(DMA)(3)] (1) (BTC3-= benzene-1,3,5-tricarboxylate, DMA =N,N-dimethylacetamide) obtained from the reaction between Co(2+)and H3BTC in DMA features a three-dimensionalsrsframework built of 3-connected {Co-2(COO)(3)} as secondary building units and BTC(3-)as spacers. When exposed to DMA solution of Cu(NO3)(2),1was progressively transformed into the first heterometallic Co-Cu-HKUST-1 ([Co0.14Cu2.86(BTC)(2)]) (2) of such kind via unusually solvent-mediated structural transformation and simultaneous partial transmetalation. While the mechanism for such conversion is proposed based on systematic studies,2was revealed to be an equally efficient desulfurization adsorbent as the homometallic Cu-HKUST-1 in removing thiophene (0.142 mmol S per gram of adsorbent). However, when exposed to Zn(NO3)(2)solution in DMA for longer time,1retained its framework with limited metal-ion exchange, resulting in the formation of [Co1.93Zn0.07(BTC)(Cl)(DMA)(3)] (3). Possible reasons responsible for the formation of2and3through different routes could be due to the less solubility and more thermodynamic stability of2in comparison with those of1, and the different coordination geometries which Co2+, Zn(2+)and Cu(2+)prefer.